Dual purpose agricultural compositions

ABSTRACT

A method of fertilizing a plant comprises applying to a plant an effective amount of a composition comprising a product of a salicylic acid, a potassium polyphosphite, a potassium phosphite, and a potassium phosphate. The composition may be prepared by reacting salicylic acid, ammonium hydroxide, potassium hydroxide and/or potassium carbonate, phosphoric acid, and phosphorous acid.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a continuation of application Ser. No. 14/696,977, filed Apr.27, 2015, now U.S. Pat. No. 9,266,788, which is a continuation ofapplication Ser. No. 13/912,340, filed on Jun. 7, 2013, which is acontinuation of application Ser. No. 13/538,661, filed on Jun. 29, 2012,now U.S. Pat. No. 8,461,079, which is a continuation of application Ser.No. 13/035,959, filed on Feb. 26, 2011 and claims the benefit ofprovisional Application No. 61/308,598, filed on Feb. 26, 2010.Application Ser. No. 13/912,340 is also a continuation-in-part ofapplication Ser. No. 13/094,932, filed on Apr. 27, 2011, now U.S. Pat.No. 8,216,972, which is a continuation-in-part of application Ser. No.13/035,779, filed on Feb. 25, 2011, now U.S. Pat. No. 8,193,119, whichclaims the benefit of provisional Application No. 61/308,569, filed onFeb. 26, 2010. Application Ser. No. 13/912,340 is also acontinuation-in-part of application Ser. No. 13/544,064, filed on Jul.9, 2012, now U.S. Pat. No. 8,585,796, which is a continuation ofapplication Ser. No. 13/308,681, filed on Dec. 11, 2011, now U.S. Pat.No. 8,221,516, which is a division of application Ser. No. 13/019,564,filed on Feb. 2, 2011, now U.S. Pat. No. 8,088,191, which is a divisionof application Ser. No. 11/349,064, filed on Feb. 6, 2006, now U.S. Pat.No. 7,887,616, which claims the benefit of provisional Application No.60/650,378, filed on Feb. 4, 2005. Each of these prior applications isincorporated by reference in its entirety.

FIELD

The present disclosure relates to agricultural treatments, and morespecifically to pesticidal and nutritional application.

BACKGROUND

Plants are subject to a wide variety of fungal and bacterial diseasesand damage by insects. Fruit bearing plants, in particular citrus treesare subject severally totally destructive diseases, Xanthomonasaxonopodis pv. Citri (Xac), Asiatic citrus canker (Canker) andHuanglongbing/Citrus Greening (Liberibacter asiaticus (CGD), which isvectored by the Asian citrus psyllid (AsCP), Diaphorina citri Kuwayama(Greening).

Citrus canker and Greening are particular problems for citrus crops asis the insect vector, psyllids. Presently, Greening is prevalentworldwide throughout all the countries that produce citrus; there is noknown cure. The official sometimes mandated, scientific worldwiderecommendation is for trees identified and affected with Greening to beremoved and burned. In the case of Canker, hundreds of thousands ofacres worldwide have been destroyed and removed because of the effectsof the disease. Presently the only official recommendation by thescientific community, is prophylactic by spraying surface protectants onthe plant tissue of citrus trees, which has little or no because thesesurficial fungicidal sprays are easily washed off by moisture.

It would be desirable to have products that can be applied to fruitbearing plants that will systemically stop or effectively retard damagecaused by fungal and bacterial diseases and insects while at the sametime also fertilizing these plants and allowing the plants to rejuvenatewhile being healed and then continue to bear fruit, preferably inincreased yields.

A one product “weed and feed” technology has long been available in theturf industry as a superior method to control weeds and promote plantgrowth; doing two jobs simultaneously and saving the cost of separateapplications. If just a nutrient was applied separately to weed infestedturf, both the turf and the weeds would benefit more than the turf.Likewise, if a costly second herbicide application was made appliedseparately the target weeds would be controlled but the grass would notgrow quickly enough to outgrow the next crop of weeds.

Phosphorus (P) is one of the major elements required by all livingspecies to grow and develop. When the element phosphorus is oxidized tothe fullest extent possible, its acid is termed phosphoric acid, [H₃PO₄or PO(OH)₃], and the salts of phosphoric acid are termed phosphates,e.g. K₂HPO₄. With phosphorus in a slightly less oxidized form, thephosphorus in the acid form is termed phosphorous acid, [H₃PO₃, orHPO(OH)₂], and the salts of phosphorous acid are termed phosphites, e.g.K₂HPO₃. Phosphites are marketed either as an agricultural fungicide,bactericide or without research data as a superior source of plantphosphorus (P) nutrition.

Polyphosphates are sometimes referred to as pyrophosphates. Additionalphosphate ions may react further with the polyphosphate, P₂O₇ ⁻⁴, toform longer polyphosphates and, in general, there is a mixture ofvarying polymer chain lengths in any given sample. The presence of someproportion of polyphosphates in fertilizer is useful for purposes ofsequestration of impurities, as suspensions aids, and for makingphosphorus more available to plants.

On the other hand, the lower valent phosphite (PO₃ ⁻³), has never playedan important role in the commercial fertilizer industry.

The analysis of polyphosphite content in a composition is difficultbecause all common wet chemical methods for determination of phosphitedepend upon reagents that first convert phosphite to phosphate. Thesereagents will break up any polyphosphite molecules present in thecomposition into individual phosphite ions. Polyphosphite, therefore,cannot be detected or quantified by the routine wet chemical methods.For instance, iodine solutions are used to oxidize inorganic phosphitesfor subsequent analysis as phosphate. Iodine will breakup any phosphitepolymer present and the polyphosphite will not be detected. Similarly,commercial labs which analyze fertilizers do not report phosphite levelsbut rather report them as phosphate. Also, during analytical proceduresrequiring heat, phosphites would typically be slowly converted tophosphate unless precautions are taken to prevent oxidation by excludingair. Furthermore, at elevated temperatures polyphosphites can beexpected to hydrolyze to ordinary phosphite ion, analogously to thehydrolysis of polyphosphates under similar conditions. Accordingly,physical methods such as nuclear magnetic resonance (NMR), high pressureliquid chromatography (HPLC), liquid chromatography, mass spectrometry(MS), and other physical molecular weight determining methods are usefulmethods for characterizing polyphosphites.

NMR provides a unique method of detecting phosphite because in mostcases, and particularly when in solution, it exists with a hydrogenattached to the phosphorus atom (HP0₃ ⁻²).

Sophisticated NMR instruments, such as the Varian VXR-3005 spectrometer,can not only detect and measure ³¹P but can also simultaneously performmeasurements on atoms such as hydrogen attached to phosphorus or carbonby transfer polarization. Such an instrument can, therefore, detect andmeasure phosphite in the presence of other phosphorus species withoutambiguity.

Potassium phosphite would be particularly useful because it wouldprovide the second important nutrient of the three critical plantnutrients, potassium. Moreover, a polyphosphite can be expected toprovide the sequestration and slow release advantages known withpolyphosphate, although phosphites are more active fungicides.

Phosphites are highly selective, non-toxic fungicides active againstnumerous fungal pathogens, and provide both protective and curativeresponses against such plant disease isolates of Phytophthora,Rhizoctonia, Pythium, and Fusarium, and other plant diseases—buttypically not against bacterial diseases. Additional informationregarding phosphorus-based fertilizers is presented in the “Backgroundof the Invention” section of U.S. Pat. No. 7,887,616, the contents ofwhich are hereby incorporated by reference.

Current commercial methods for making salt compositions from phosphoricacid and phosphorous acid (Phosphorus (P) acids), for foliar applicationplants are described in the “Background of the Invention” section ofU.S. Pat. No. 8,193,119, the contents of which are incorporated byreference.

SUMMARY

The invention discloses a pesticide and nutrient solution combinationwhich will enhance plant growth more so than if each material is appliedseparately.

The novel composition of this invention comprises a blend of: (1) anaqueous salicylate solution; (2) an aqueous reaction mixture; andoptionally, (3) an aqueous complexed potassium acetate solution.

The aqueous salicylate solution component (1) comprises salicylic acidreacted in an aqueous media with ammonium hydroxide and potassiumhydroxide. It is well known that ammonium hydroxide and potassiumhydroxide cannot be mixed together; otherwise an undesirable reactionwill occur. In mixing with salicylic acid, it is first mixed withammonium hydroxide, allowed to react and thereafter followed by additionof potassium hydroxide, or vice-versa.

The aqueous salicylate solution comprises 10-20% wt. salicylic acidsubstantially reacted in an aqueous media with a sufficient amount ofbetween about 1 to 2 parts ammonium hydroxide and potassium hydroxidecombined.

The aqueous reaction mixture component (2) is made from the reaction of:a) an acid solution comprising about 10-50 parts phosphorous acid andabout 50-90 parts phosphoric acid; and, b) aqueous potassium hydroxideor ammonium hydroxide where the ratio of monovalent cations tophosphorus in mole rations is between about 1:1 to about 2:1. Thereaction mixture formed comprises potassium phosphates, potassiumpolyphosphate, potassium phosphites, and potassium polyphosphite andpotassium phosphate phosphite copolymers. ‘The aqueous reaction mixturecomponent (2) is blended under pressure in a continuous system such as apipe reactor and thereafter rapidly cooled.

When an amount, concentration, or other values or parameters are givenas either a range, preferred range, or a list of upper preferable valuesand lower preferable values, this is to be understood as specificallydisclosing all ranges formed from any pair of any upper range limit orpreferred value and any lower range limit or preferred value, regardlessof whether ranges are separately disclosed. Where a range of numericalvalues is recited herein, unless otherwise stated, the range is intendedto include the endpoints thereof, and all integers and fractions withinthe range. It is not intended that the scope of the invention be limitedto the specific values recited when defining a range.

DEFINITIONS

In the context of this disclosure, a number of terms are utilized.

The term “comprising” is intended to include embodiments encompassed bythe terms “consisting essentially of” and “consisting of”. Similarly,the term “consisting essentially of” is intended to include embodimentsencompassed by the term “consisting of”.

The term “potassium phosphate-phosphite copolymer(s)” means copolymersof potassium phosphates and potassium phosphites.

The term “aqueous potassium polyphosphite solution” means an aqueousmixture formed by the process of this invention wherein aqueousphosphorous acid is reacted with potassium hydroxide and comprisespotassium ortho and polyphosphites, mono-potassium phosphite, and ordi-potassium phosphite and forms a pesticidal and/or nutrient solution.

The term “reaction mixture” means an aqueous mixture formed by theprocess of this invention comprising potassium phosphate, potassiumpolyphosphates, potassium phosphite, potassium polyphosphites andpotassium polyphosphate and polyphosphite copolymers.

The nutrients present, force quick vigorous growth of the crop, whileenabling the crop to more effectively compete with pests held in checkby the pesticide.

Plant spray compositions are disclosed that provide in one applicationfungicidal and/or bactericidal, and/or herbicidal and/or insecticidalprotection to plants. Plant health is restored by providing foliarapplied nutrients directly to the plants to provide energy forphotosynthesis. This is beneficial particularly where root nutrientabsorption has been comprised because of disease, chemical or mechanicalplant injury or other environmental factors.

The combination of applying a pesticide with a nutrient solutionsynergistically enhances more growth than if each material is appliedseparately. The nutrients present force quick, vigorous growth of thecrop, while enabling the crop to more effectively compete with pestsheld in check by the pesticide.

Because a concentrated acid solution is combined with a concentratedaqueous potassium hydroxide in a pipe reactor, this creates anexothermic reaction under pressure greater than atmospheric and resultsin a product comprising phosphates, polyphosphates, phosphites,polyphosphites and phosphate phosphite copolymers. Water is released assteam. Thereafter, the product is rapidly cooled to below 35° C. toabout 65° C. to reduce the hydrolysis reaction or other degradation ofthe polyphosphates and polyphosphites formed. It is believed any excesswater present will result in an undesired breakdown of the phosphatephosphite co-polymers. Preservation of the polyphosphates,polyphosphites, and phosphate phosphite copolymers is critical becausethese components act respectively as a fertilizer andbactericide/fungicide when an effective amount of the reaction mixtureis first diluted and then applied to plants. The process for making thereaction mixture is described in U.S. Pat. No. 8,216,972, the contentsof which are incorporated by reference.

Optionally, aqueous complexed potassium acetate can be added to theblend of components (1) and (2).

When making the reaction mixture component (2), dry phosphorous acid canbe dissolved directly into a concentrated liquid phosphoric acid tominimize wasteful “added free water”, which would hinder thepolymerizing reaction. Thus, a concentrated solution is formed havinggreater reactivity to form phosphorous acid polymers.

The phosphoric acid used can be in any commercial or practicalconcentration, usually from 75% to a 115% H₃PO₄ concentration. Aconcentration over 96% is considered to be super phosphoric acid;however, the preferred concentration is from 85% to 105% for practicalcommercial acid purchase availability, handling and storage advantage.The phosphorous solution can be in the range of 1-99 parts phosphoricacid to 99-1 parts phosphorous acid, preferably about 90-50 partsphosphoric acid to 10-50 parts phosphorous acid. The concentratedpotassium hydroxide used is between about 40-60% wt.

An unexpected and important advantage of the process for forming areaction product is that polyphosphate and polyphosphite can be preparedsimultaneously. The presence of both acids in the process provides forthe formation of copolymers, that is, polymers containing both phosphiteand phosphate groups. Such copolymers are new materials and not simply amixture of polyphosphite and polyphosphate. However, chemical analysisof such polymers is difficult.

Another aspect of the invention is a process for the application of aneffective amount of each of the above components to plants, such ascitrus plants or other fruit bearing plants, vegetable plants, turf andornamental plants and field crops in order to provide fungicidal,bactericidal and insecticidal protection and fertilization to plantsthereby improving yields.

The novel process of this invention provides a number of advantages overmethods taught in the art. In a single step process, a fungicidal andfertilizer composition is prepared having polymeric components that havea higher analysis with long term storage stability allowing thecomposition to remain, as a clear solution, in storage for extendedperiods of time without “salting out”, and remaining in a clear solutionlonger than conventionally produced orthophosphorous products. Thepolymerized products of this invention, and can be readily blended withother components, particularly sequestering inorganic metal compoundssuch as Copper, Iron, Manganese and Zinc to form higher analysis, stablecompositions that reduce and many cases eliminate fungicidal activity ona wide variety of plants and crops and provides fertilizer components toplants and crops in particular, a polyphosphate which is well known tobe beneficial to plants. Further, there is significantly less foliageburn caused when the products of this invention are applied directly toplants, because of the polymers present in the solutions of theinvention. The polyphosphate and polyphosphite compounds of thisinvention are also capable of forming soluble complexes with metalimpurities by a sequestration process; also, the compositions haveactivity as a pesticide.

An important aspect of the novel process, which has not been previouslyrecognized, is that dissolving orthophosphorous acid directly inorthophosphoric or super polyphosphoric acid without additional of waterprovides a high concentration of highly reactive acid when used in theprocess is capable of producing polymeric compounds. Less water ispresent in the novel process thereby concentrating the acid favorablyfor the formation of polyphosphorus compounds. Thus, polymer formationis facilitated and increased and the exothermic reaction temperature ishigher causing an additional release of water to provide a highconcentration reaction mixture and conversion containing phosphate andphosphite polymers, along with residual ortho phosphate and orthophosphite compounds. Further, degradation by hydrolysis of the potassiumpolyphosphites and related polymers is significantly reduced. With theuse of a continuous reactor in the process, the risk of a “runaway”reaction is eliminated. The unwanted formation of phosphine gas thatoften occurs in a batch reaction, and which is very difficult tocontrol, is eliminated by the complete, instantaneous reaction, and therapid cooling process to below critical phosphine formation temperaturelevels. Only evaporative steam from the heat of reaction, and thedehydration of the phosphate and phosphite moieties in this novelprocess, is harmlessly discharged to the environment.

The aqueous reaction mixture component (2) of the present compositionmay also contain potassium phosphite and at least 25-75% by weight ormore of potassium polyphosphite.

Additionally, described is a method of making a fungicidal compositionhaving fertilizer properties and containing at least about 25-75% byweight of potassium polyphosphite. The method comprises reactingphosphorous acid and potassium hydroxide in aqueous solution at atemperature of at least approximately 270 F and rapidly cooling theaqueous solution to a temperature below approximately 90 F. A morepreferred method includes making a composition consisting essentially ofpotassium polyphosphite by reacting phosphorous acid and potassiumhydroxide in aqueous solution at a temperature above 270 F and rapidlycooling the aqueous solution to a temperature below approximately 90 F.The Method may be carried out wherein reacting is conducted at betweenabout 300 F-350 F and wherein cooling is conducted at about 90 F orless.

The polyphosphite composition has fertilizer utility and a method offertilizing a plant includes applying an effective amount of thecomposition. The present invention also includes a method of treating aplant for a fungal infection, the method comprising applying aneffective amount of one of the polyphosphate compositions disclosed. Thecomposition of the present invention may also be used for treating aplant for a microbial infection, that is, of an etiology other than afungus, the method comprising applying an effective amount of thecomposition.

Moreover, the present polyphosphite composition has demonstratedeffectiveness against bacterial diseases, including the bacterial plantpathogen, Xanthomonas axonopodis pv. Citri (Xac), which is the cause ofAsiatic citrus canker, where no other cure is currently available.

In addition, Ralstonia solanacearum, a bacterial wilt infection, isvirtually 100% controlled with the present polyphosphite composition. Ithas been discovered that a unique third mode of protection, is at work,in that control of the organism is by a previously unrecognizedbacteriostatic method, rendering the pathogen unable to reproduceitself.

BRIEF DESCRIPTION OF THE DRAWINGS

Some of the features, advantages, and benefits of the present inventionhaving been stated, others will become apparent as the descriptionproceeds when taken in conjunction with the accompanying drawings,presented for solely for exemplary purposes and not with the intent tolimit the invention thereto, and in which:

FIG. 1 is a cross-sectional side elevation of an apparatus which may beused in preparing the composition according to an embodiment of thepresent invention;

FIG. 2 is a graph showing activity of the present polyphosphitecomposition against some bacterial agents of plant disease;

FIG. 3 NMR spectra for sample PFS 026, as described in example 11

FIG. 4 NMR spectra for sample PFS 030, as described in example 11;

FIG. 5 NMR spectrum for P³¹ for sample PFS 002, as described in Example9; and,

FIG. 6 is an NMR H¹ polarization transfer spectrum also for sample PFS002.

DETAILED DESCRIPTION OF EMBODIMENTS

One embodiment of the reaction of the reaction mixture used in the novelcompositions of this invention that provides bactericidal andnutritional activity comprises dissolving concentrated 99% crystallinephosphorous acid in a concentrated solution of phosphoric or superphosphoric acid to form a single super concentrate acid solution, whichis capable of higher reaction temperatures with aqueous base metalhydroxide solution/hydroxide solutions, e.g., potassium hydroxide orpotassium carbonate, in order to form high analysis potassiumphosphates, potassium polyphosphates, potassium phosphites, andpotassium polyphosphites and potassium phosphate phosphite copolymers.

An aspect of this invention that provides bactericidal activity whentreating plants in an effective amount comprises an aqueous salicylatesolution having salicylic acid reacted in an aqueous media with firstwith ammonium hydroxide and thereafter with potassium hydroxide, or inreverse order of hydroxide reaction.

Another aspect of this invention is a composition that providesfungicidal protection to plants and fertilizes plants when treated withan effective amount which composition comprises an aqueous blend of theabove aqueous salicylate solution and an aqueous reaction mixturecomprising potassium phosphates, potassium polyphosphate, potassiumphosphites, and potassium polyphosphite and potassium phosphatephosphite copolymers.

Also, as part of this invention is a composition that provides superiorfungicidal protection to plants when treated with an effective amount ofthe composition in which composition comprises an aqueous reactionmixture selected from the group consisting of potassium phosphates,potassium polyphosphate, potassium phosphites, potassium polyphosphiteand potassium phosphate phosphite copolymers or combinations thereof,and an aqueous complexed potassium acetate solution.

The composition this contains a blending of:

(1) an aqueous salicylate solution component that comprises salicylicacid reacted in an aqueous media with ammonium hydroxide and potassiumhydroxide. It is well known that ammonium hydroxide and potassiumhydroxide cannot be mixed together; otherwise an undesirable reactionwill occur. In mixing with salicylic acid, it is first mixed withammonium hydroxide, allowed to react and thereafter followed by additionof potassium hydroxide, or vice versa; and

(2) an aqueous reaction mixture component made from the reaction of: (a)an acid solution comprising about 10-50 parts phosphorous acid and about50-90 parts phosphoric acid; and, b) aqueous potassium hydroxide orammonium hydroxide where the ration of monovalent cations to phosphorousin mole ratios is between about 1:1 to about 2:1. The reaction mixtureformed comprises potassium phosphates, potassium polyphosphate,potassium phosphites, and potassium polyphosphite and potassiumphosphate phosphite copolymers. The aqueous reaction mixture component(2) is blended under pressure in a continuous system such as a pipereactor and thereafter rapidly cooled, an example of which is presentedas Example 11.

The aqueous salicylate solution (1) comprises 10-20% wt. salicylic acidsubstantially reacted in an aqueous media with a sufficient amount ofbetween about 1 to 2 parts ammonium hydroxide and potassium hydroxidecombined.

The above composition can readily be augmented by cold blending togetherurea and other nutrients thereby forming compositions that are stable,homogeneous and sprayable. These compositions are readily prepared byprescription for specific crops and specific situation and can bediluted with water if necessary when applied to plants.

The novel aqueous compositions synergistically and effectively feedcrops, eliminate the deleterious effects of fungal diseases, bacterialdiseases and insect damage and improve yields than if a pesticide andnutrient solution was used alone. After a period of time and uponexposure to the elements, the potassium polyphosphates andpolyphosphites oxidize to provide fertilizer components to the crop,i.e., potassium and ortho-phosphorus. Furthermore, each of the novelaqueous compositions can be blended with components, such as, urea,nitrates or other ammonical compounds to provide a nitrogen componentand also with effective amounts of secondary nutrients such as, calcium,magnesium, sulfur, and micronutrients, such as, boron, copper, iron,molybdenum, manganese and zinc to form a high quality fertilizercomponent. Stable clear and sprayable compositions are formed that havea relatively long shelf life.

The novel aqueous compositions can be cold blended with water for foliarspray application by the grower. The composition can be used in aconcentrated form for metering and injection into a spray that isapplied to a crop. Typically effective amounts are applied to cropsdepending on the crop and the problems associated with the crop that arecorrected by the compositions of this invention.

The following are examples of synergistic treatment using my pesticideand nutrient solution combination

Example 1

A test of the novel Dual Purpose Agricultural Composition (DPAC) of thisinvention was conducted in Martin County Florida in a 30 hectare blockof Valencia oranges that had been abandoned and had no commercial valuedo to the sever incidence of Huanglongbing Citrus Greening Disease(HLB), which is transmitted by psyllids, which are small piercingsucking insects. HLB symptoms include small yellow leaves with a mottledor blotchy appearance and yellow veins exhibiting mineral deficienciessuch as Manganese and Zinc, twig and branch dieback, sparse, small fruitthat is abnormal in appearance and fails to color properly, thus thename greening, with aborted seeds and poor juice quality and finallyrapid degeneration into a non-productive state. Mortality can occurwithin three years. Two different application rates of DPAC were appliedin two partial sections of the block, seven liters per hectare and 14liters per hectare. Micronutrients and other pest control materials wereadded to the tank mix and applied. Within four weeks of the initialapplication of DPAC, it was apparent that the all the trees began torecover as evidenced by new growth, on the barren twigs that had begunto die back. Within six months the recovery was readily obvious, treesbegan normal growth, and a total care program was restored.

Example 2

In an 800 hectare citrus grove located in Felda, Fla., six trees werediagnosed with Xanthomonas citri subsp. Citri., bacterial citrus canker,is a leaf, fruit, and stem blemishing disease, by the bacterialpenetration of the stomatal pores. A 14 liter per pectate of DPAC wasapplied, together with other tank mix materials, and further spread andcontrol of the canker was achieved. It was also noted that one of thetrees had also been diagnosed with HLB and an inspection of the entiregrove revealed a 90% HLB infection rate and treated with DPAC, fromwhich no trees suffered mortality and the grove is returning to normalproductivity.

Example 3

A commercial size test was undertaken in South Florida in order to testthe efficacy of the NC of this invention in a citrus grove with 70% leafloss rate, as compared to the recommended program of tree removal, in anadjoining citrus grove also infected with HLB. There were ultimatelyfour treatments of 10 liters per hectare, along with micronutrientsadded to the tank mix, of DPAC. Within four months of initial treatmentof DPAC, tree health and vigor was restored, as new leaf growth wasobserved throughout. The new canopy growth nearly doubled the tree sizeand a normal fruit crop was set. The grower reported that yields hadreturned to normal, while the adjoining grove, untreated with DPAC,continued to decline with tree removal continuing.

Example 4

A replicated research trial was conducted in order to ascertain which ofthe sprayed materials was achieving the results of examples one, two,and three, by a process of elimination conducted in seven differentfoliar spray regimes. It was determined that the DPAC of this inventioncould not be eliminated, in order to achieve control results of HLB,while other materials could be eliminated.

The aqueous reaction mixture component (2) is based on the “DetailedDescription of the Preferred Embodiment” section of U.S. Pat. No.8,221,516, the contents of which are hereby incorporated by reference.

The invention will now be described more fully hereinafter withreference to the accompanying drawings, in which preferred embodimentsof the invention are shown. Unless otherwise defined, all technical andscientific terms used herein have the same meaning as commonlyunderstood by one of ordinary skill in the art to which this inventionpertains. Although methods and materials similar or equivalent to thosedescribed herein can be used in the practice or testing of the presentinvention, suitable methods and materials are described below. Anypublications, patent applications, patents, or other referencesmentioned herein are incorporated by reference in their entirety. Incase of conflict, the present specification, including any definitions,will control. In addition, the materials, methods and examples given areillustrative in nature only and not intended to be limiting.Accordingly, this invention may, however, be embodied in many differentforms and should not be construed as limited to the illustratedembodiments set forth herein. Rather, these illustrated embodiments areprovided so that this disclosure will be thorough and complete, and willfully convey the scope of the invention of those skilled in the art.Other features and advantages of the invention will be apparent from thefollowing detailed description and from the claims.

Apparatus for Manufacture of the Aqueous Reaction Mixture (2)

A preferred embodiment for the manufacture of component (2) of presentinvention employs the cross-pipe reactor described in U.S. Pat. No.4,724,132 (the '132 patent) in combination with a down-stream mixerwhich is a static in-line mixer, the static in-line mixer can beextremely short or, in fact, the static inline mixer could comprise theentire length of the pipe 60 as shown, in which case the static in-linemixer would essentially deliver product into the receiving tank 70 andFIG. 1 would be modified to basically delete pipe 60. The primarycriterion which would set the length of the static in-line mixer, if itis used, is to insure that reaction is substantially complete prior tothe time the product enters the receiving tank 70 as shown in FIG. 1.Generally speaking, if the static in-line mixer (or some other mixer) isnot used downstream the cross-pipe reactor the length of the pipe 60should be increased to insure substantially complete reaction with adecrease in the length of pipe 60 if a static in-line mixer is used. Theexact length of the static in-line mixer and/or the pipe 60 can easilybe determined by standard chemical engineering practices.

The excellent mixing, polymerization and temperature obtained with thecross-pipe reactor creates a greater potassium hydroxidesolution/acidulation surface area, and insures good conversion of thepotassium compound(s) to polyphosphite salt. Acidulation is, of course,the process of adding acid, and generally the amount of mineral acid,phosphorous acid, is specified with respect to the amount of potassiumhydroxide. This can easily be established by one skilled in the art.

As indicated, even more pronounced effects are obtained with theaddition of the static in-line mixer down-stream from the cross-pipereactor. A typical static in-line mixer useful in the present inventionand, in fact, the one that has been used to date, is disclosed in U.S.Pat. No. 4,093,188 to Horner, hereby incorporated by reference. Theparticular static in-line mixer disclosed has stationary bafflesproviding sinuous, non-parallel spiraling flow paths to promote thoroughand homogeneous intermixing of fluids. It is not mandatory to use thatprecise static in-line mixer and other static in-line mixers, also knownas stationary baffle mixers or interfacial surface generators, can beused. For example, it is believed that stationary baffle mixers orinterfacial surface generators as disclosed in U.S. Pat. Nos. 3,190,618;3,620,506; 3,643,927; 3,652,061; 3,923,288; 3,947,939 and Reissue No.28,072 could be used with equal success, and all of these patents arealso incorporated by reference. Other mixers could likely be usedinstead of a static in-line mixer, for example, as can be appropriatelyselected by one skilled in the art from Chemical Engineers' Handbook,John H. Perry, Editor, Third Edition, McGraw-Hill Book Co., Inc., pp.1195-1231

After the reactants have passed through the cross-pipe reactor 10, themixer 50 and pipe 60, the reacted mixture is conveniently dischargedinto a receiving tank 70. Generally, it is preferable to substantiallycomplete reaction prior to introduction of the product into thereceiving tank 70. As one skilled in reaction kinetics will appreciate,there will be some slight amount of reaction in the receiving tank 70,but this is not of consequence if any reasonable amount of care isexercised over the process control, as would be understood by a chemicalengineer. The discharge is usually above the level of the liquid in thereceiving tank 70 in order to achieve faster flash cooling. If thedischarge is below the liquid level, reducing to some degree the coolingcapacity, the conversion ratio from metal hydroxide solution to salt isslightly improved. As will be appreciated by one skilled in the art, theuse of a receiving tank is merely a convenient means to use a cool,large mass of product to inexpensively cool the product received frompipe 60. The composition should be cooled to approximately 90 F., orless, as rapidly as possible. Any conventional means could be used toachieve this cooling effect.

The determination and adjustment of optimum reaction parameters will bewell within the skill of the chemical engineer. The product can berecirculated from receiving tank 70 through cooling means (not shown)via pump 90. If desired, some product can be sent to storage via line100 but normally the greater volume is recirculated over a packed column110 through which air is blown by fan 120 in order to cool the productprior to storage. Also, as one skilled in the art will appreciate,pumping means are provided throughout the system as needed; these areconventional and are not shown. Further, the skilled will recognizethat, since a mineral acid is being used, conventional process equipmentresistant to acidic conditions will be used, typically stainless steel.

Description of the Process

Evidence of the makeup of the composition is found in NMR results ofseveral samples and from chemical tests. Samples were prepared by theuse of the apparatus of the present invention as shown in FIG. 1 anddescribed below. NMR analysis was conducted by Process NMR Associates,LLC, using a Varian VXR 300-S Spectrometer. Spectra were recorded andthe position of the peaks noted in terms of parts per million of fieldstrength (ppm) relative to the standard inorganic phosphate peak.Simultaneously, the samples were examined for the hydrogen atom attachedto the phosphorous atom using the transfer polarization technique.Concentration, different counter-ions, such as ammonium, sodium, orpotassium can cause a small change in position of the peaks, thereforethe exact position of the peaks in a given spectrum is not definitive.However, the relative position of one peak to another, such as phosphateversus phosphite, is useful. Potassium phosphite alone exhibits a singlesharp peak for the P³¹ atom and a correspondingly sharp peak in thetransfer polarization spectrum for the H¹ atom that is attached to the Patom of all inorganic phosphites. To the contrary, no correspondingtransfer polarization spectrum for H¹ is found for polyphosphites, whichclearly indicates that there are no longer H¹ atoms attached to thephosphorus and that the starting material, HP0₃ ⁻², has been chemicallychanged. In addition, in confirmation of polymeric character, the peakis no longer sharp (half width of about 10 to 20 Hz) but very broad(half width of about 30 to 100 Hz). The breadth of such P^(f1) NMRpeaks, at a given field strength, is the result of the differentpositions of phosphorus atoms in the polymer and the different molecularweights of oligomers. Accordingly, each atom yields a signal indicatingits unique environment and, since the signals are only slightlydifferent, the result is a broader peak. In the case of phosphite andpolyphosphite, the peak positions are very near each other and a broadpeak can cover over a smaller narrower peak. Under the differentconditions in the various examples of the present invention, thecomposition prepared may contain more or less potassium polyphosphitewith the balance being simple potassium phosphite. However, severalsamples have been prepared by this invention that give no detectableresponse for P31-H1 in transfer polarization NMR analyses, therebyindicating that the samples are nearly 100% polymerized by P03-3,polyphosphite. Furthermore and analogous to polyphosphate chemistry, ishas been found that the composition prepared by the present inventionreadily generates free acid when they are heated above ambienttemperature thereby providing further confirmation of the proposedstructure, as illustrated in FIG. 2. The amount of free acid continuesto increase with time as the composition is held at an elevatedtemperature.

A most preferred embodiment in a continuous process of the presentinvention will be described with reference to the FIG. 1 and comprises ametal hydroxide solution, e.g., potassium hydroxide solution, as anaqueous solution reacted with a mineral acid, e.g., phosphorous acid,with water being added as necessary to adjust specific gravity. Themetal hydroxide solution is pumped into port 20 of the cross-pipe tee10, the mineral acid is pumped to port 30 and the water is pumped intoport 40. Reaction begins on contact of the metal hydroxide solution andmineral acid and the mixture of the reactants is forced substantiallyimmediately into the static in-line mixer 50 where reaction continues tooccur. The rate of total feed is controlled so that the temperature astaken about midway up the pipe 60 above the in-line mixer 50 ismaintained at a desired level, and preferably at about 300 degreesF.+/−0.50 degrees. Generally speaking, the reaction continues in thepipe 60. Since the reaction of the present invention is exothermic,external heat need not be supplied to the system. As a general practice,I simply measure the temperature about one-half way up the distance ofthe pipe 60 as shown in the FIG. 1 by temperature indicator 130.However, the temperature could easily be measured anywhere between thecross-pipe reactor and discharge into the receiving tank 70 as shown inFIG. 1. The ratio of the potassium hydroxide solution to phosphorousacid fed is adjusted to maintain product pH specification at the desiredlevel, depending on the type of product being manufactured. The rate ofwater addition is controlled to maintain the desired product specificgravity. Product specific gravity is a relatively precise number and istypically set by the tolerances of fertilizer control laws. It can befreely selected by one skilled in the art. Various examples follow,including one example of a prior art batch process which is inadequatefor use in the present invention.

Example 5

This example is a batch process and represents prior art methods, ratherthan a method of the present invention. It is presented here to show howthe prior art is unable to achieve the results provided by the presentinvention.

Into a 5,000 ml stainless steel laboratory blend tank outfitted with anelectric driven propeller-type mixer, a 2,000 gram batch of a 70%solution of phosphorous acid was dissolved and prepared from 1,414 gramsof 99% white, crystalline phosphorous acid, into 586 grams of distilledwater. A 70% solution of phosphorous acid is the normal concentrationcommercially available that is typically used in the production ofphosphorous acid products. Heat was applied in order to keep thetemperature at 70 degree. F. throughout the process and the mixture wasstirred vigorously for approximately 10 minutes to obtain a uniform,clear solution of phosphorous acid. This solution was then poured offinto a flak and stoppered. Of this solution, 918 grams was weighed intoanother flask and stoppered. 1,239 grams of 50% KOH was weighed andstored in a separate flask, both weighed products being of sufficientquantity in order to blend a 2,000 gram batch of a typical potassiumphosphite product by the batch method, as known by those practicing inthe art. There was a negative −157 gram imbalance of water which wasexpected to evaporate off as a result of the exothermic reaction. The1,239 grams of KOH was poured into the above describe 5,000 ml tank, andagitation begun. At this point the laboratory ventilation system shouldbe engaged and the technician should wear proper laboratory safetyattire, including goggles, for handling hazardous materials. Then, theaddition of the 918 grams of acid was started with continuous agitation.The rate of addition of acid was maintained as fast as possible butwithout causing vigorous boiling of the water. During the addition ofthe first 200 grams of acid, the batch began to boil vigorously, withthe temperature reaching about 150 degree F. Upon cooling sufficiently,another 200 grams of acid was added slowly to the boiling point againcontinuously from the mixture. When most of the calculated amount ofacid had been added, a very faint garlic-like odor was detectable,indicative of the formation of phosphine. The lab was immediatelyvacated until it was determined that the mixture had stopped boiling andthat the lab had been properly ventilated. Personnel reentering the labdonned protective masks. It was not possible to complete the batchwithout exceeding about 130 degree F., without the material boiling overand out of the tank, and without the further risk of producing phosphinegas. The final pH was adjusted to 6.8 and the mixture was cooled in awater bath.

Example 6

This example describes the general process employed in the invention, inthe temperature range as used also in examples 8 and 10. A run wascarried out using equipment as shown in the above described crosspipereactor including a special mixing device, i.e., an open cross-pipereactor with a static in-line mixer, as disclosed in U.S. Pat. No.4,093,188 to Horner. It is commercially available under the trade nameSTATA-TUBE and is a motionless mixture manufactured by TAH Industries,P.O. Box 178, Imlaystown, N.J. 08526, (2″ L.D. times.96″ length). In theExamples herein the runs were on a commercial scale using a cross teereactor where the ports had an inner diameter of about 2 inches″ and thepipe was about 96″ in length having an inner diameter the same as thecross tee reactor ports. Obviously these dimensions are not restrictiveand smaller and/or larger devices can be used. All process lines werestainless steel. Reactants were pumped into the cross-pipe injectionports as follows: a 50% solution of potassium hydroxide at a rate ofapproximately 21 gallons per minute (port 20), and 70% phosphorous acidat a rate of 15 gallons per minute (port 30). Water at a rate ofapproximately 3 gallons per minute was injected directly into thereceiving tank, in order to attain the highest pipe temperaturepossible. The reaction product was simply flowed into a receiving tankabove the liquid level for ease of operation. During the run frequentsamples were taken from the tank for pH and specific gravity checks, andacid and water flows were adjusted to maintain these values at thedesired levels, i.e., pH 6.8, specific gravity 1.45 (these values arethe same in the following Examples unless indicated to the contrary).Acidulation and conversion were thus controlled. During the run thetemperature at the midpoint of the pipe fluctuated from 260 degrees F.to 275 degrees F. The reactionary product entering the receiving tankwas instantly cooled to about 115 degrees F. and was pumped to afinished product storage tank at a rate of approximately 33 gallons perminute. As a result of the evaporative cooling process taking place,voluminous steam plume was continuously emitted, and sampled for anytrace of garlic like odor, and none was detected.

Example 7

Using the process of Example 6, the reactants were introduced at lowerrates, sufficient to keep the temperature at the midpoint of the pipebelow 200 degree F. and small portion of the resulting composition wasimmediately brought into the laboratory and packaged for rapid shipmentto NMR Associates, LLC in Connecticut for testing by NMR. The NMRanalysis revealed strong narrow peaks both for P³³ and H¹, which isindicative of the presence of the inorganic salt potassium phosphite.

Example 8

A run was carried out using the process of Example 6 where thetemperature at the midpoint of the pipe was between 260 degree F. and275 degree F. and a small portion was immediately brought into thelaboratory and packaged for rapid shipment to NMR Associates, LLC inConnecticut for NMR analyses. The NMR analysis revealed a single broadstrong peak for P.sup.31 and only small evidence of H¹ attached to P³¹under the polarization transfer test, which indicates that most of theinorganic potassium phosphite had been converted to polyphosphites butthat some monophosphite remained.

Example 9

The process of Example 6 was followed, where the temperature at themidpoint of the pipe was maintained between about 270 degree F. and 285degree F. A small portion was immediately brought into the laboratoryand packaged for rapid shipment to NMR Associates, LLC in Connecticutfor NMR analyses; this was labeled sample PFS 002. As shown in FIGS.5-6, the NMR analysis revealed a single broad strong peak for P³′ but noevidence of H¹ attached to P³¹ under the polarization transfer. Thisresult indicates that essentially all of the inorganic potassiumphosphite had been converted to polyphosphites.

Example 10

The process of Example 6 was carried out, but where the temperature atthe midpoint of the pipe was maintained between about 260 degree F. and275 degree F. Eight days later, a five-gallon sample was taken from thestorage tank and portions were subjected to heat treatment at varioustemperatures as follows. The sample had a specific gravity of 1.46, a pHof 6.5, and the dry solids content was about 53%. The NMR showed a largenarrow peak for P³¹ and also a significant peak for H¹ under transferpolarization. A portion, 232 g., was heated over a period of 13 minutesin an open stainless steel pan until it boiled at 116 degree C. Weightmeasurements showed a loss of 53 g of water. Further hearing for aperiod of 15 minutes resulted in an additional loss of water of 33 g andthe boiling point climbed to 145 degree C. The pH was 3. Another portionof 223 g of the original sample was heated in a similar manner but forless time so that the solution remained homogeneous. The pH was 4.

These experiments showed that free acid was being liberated uponheating, which is to be expected when hydrolysis of polyphosphiteoccurs. These data are consistent, indicating a sample containing amixture of potassium phosphite (monomer) and polyphosphites.

Example 11

A mixture of phosphoric acid and phosphorous acid was prepared for usein the reactor of the present invention. Five hundred pounds (500 lb) ofsolid 99% phosphorous acid was dissolved in 1500 lb of 75% phosphoricacid in order to increase the concentration of reactants by reducing theamount of water, and so as to subsequently increase the reactiontemperature. This acid mixture was reacted with a 50% solution ofpotassium hydroxide, the reaction expected to yield a mixture ofpotassium phosphate and potassium phosphite. The test run lastedapproximately 3 hours.

The conditions of the reaction were varied over this period of time inorder to study the effect of operational parameters. Five differentconditions were studied. A small sample (7A) was withdrawn after eachchange in the reaction conditions after the system had stabilized.Sample number PFS026 was obtained when the reaction temperature wasabout 265 degree F., the pH was 8.22, the specific gravity was 1.475,and the sample temperature was 105 degree F. The NMR spectra for thissample are shown in FIG. 3. The P³¹ spectrum shows two sharp peaksindicative of potassium phosphate and potassium phosphite. The H¹spectrum for the hydrogen attached to the phosphorous atom, obtained bypolarization transfer, confirms the presence potassium phosphite asexpected.

Sample PFS030 (7B) was obtained when the reaction temperature was about300 degree F., the pH was 7.6, the specific gravity was 1.44, and thesample temperature was 100 degree F. The NMR spectra are shown in FIG.4. Surprisingly, the P^(f1) spectrum shows a very broad peak consistentwith formation of polymer. The spectrum also shows small peaks at thetop of the broad peak indicative of small amounts of unreacted potassiumphosphate and potassium phosphite. Also surprisingly, the H¹polarization transfer spectrum shows an absence of hydrogen atomsattached to the phosphorous atom and which clearly indicates that anunexpected chemical reaction has resulted in almost complete polymerformation.

Accordingly, in the drawings and specification, there have beendisclosed typical preferred embodiments of the invention, and althoughspecific terms are employed, the terms are used in a descriptive senseonly and not for purposes of limitation. The invention has beendescribed in considerable detail with specific reference to theseillustrated embodiments. It will be apparent, however, that variousmodifications and changes can be made within the spirit and scope of theinvention as described in the foregoing specification and as defined inthe appended claims.

That which is claimed is:
 1. A method of fertilizing a plant, the methodcomprising applying to a plant an effective amount of a compositioncomprising a product of a salicylic acid, a potassium polyphosphite, apotassium phosphite, and a potassium phosphate.
 2. The method of claim1, wherein the composition further comprises a hydrolyzed potassiumpolyphosphite.
 3. The method of claim 1, wherein the composition furthercomprises a potassium polyphosphate.
 4. The method of claim 3, whereinthe composition further comprises a hydrolyzed potassium polyphosphate.5. The method of claim 1, wherein the composition further comprises apotassium polyphosphate and a phosphate/phosphite copolymer.
 6. Themethod of claim 1, wherein the plant is infected with at least one ofbacterial wilt infection, citrus canker disease, and citrus greeningdisease.
 7. The method of claim 1, wherein the salicylic acid is asalicylate.
 8. A plant fertilizer composition comprising a salicylicacid based product, a potassium polyphosphite, a potassium phosphite,and a potassium phosphate.
 9. The plant fertilizer composition of claim8, further comprising a hydrolyzed potassium polyphosphite.
 10. Theplant fertilizer composition of claim 8, further comprising a potassiumpolyphosphate.
 11. The plant fertilizer composition of claim 10, furthercomprising a hydrolyzed potassium polyphosphate.
 12. The plantfertilizer composition of claim 8, further comprising a potassiumpolyphosphate and a phosphate/phosphite copolymer.
 13. The plantfertilizer composition of claim 8, wherein the salicylic acid basedproduct is a salicylate.
 14. A method of fertilizing a plant, the methodcomprising applying to a plant an effective amount of a compositioncomprising a potassium phosphate and a potassium phosphite, thecomposition being prepared by reacting salicylic acid, ammoniumhydroxide, potassium hydroxide and/or potassium carbonate, phosphoricacid, and phosphorous acid.
 15. The method of claim 14, wherein thecomposition comprises a salicylic acid based product and a potassiumpolyphosphite.
 16. The method of claim 15, wherein the salicylic acidbased product is a salicylate.
 17. The method of claim 14, wherein thecomposition comprises a hydrolyzed potassium polyphosphite.
 18. Themethod of claim 14, wherein the composition comprises a potassiumpolyphosphate.
 19. The method of claim 18, wherein the compositioncomprises a hydrolyzed potassium polyphosphate.
 20. The method of claim14, wherein the composition comprises a potassium polyphosphate and aphosphate/phosphite copolymer.
 21. The method of claim 14, wherein theplant is infected with at least one of bacterial wilt infection, citruscanker disease, and citrus greening disease.